Facebook CEO Mark Zuckerberg and his wife scored the No. 2 spot on a list of the biggest charitable givers in the United States last year, thanks to their record $499 million donation to the Silicon Valley Community Foundation, according to a report Monday that points to a growing interest among the super-rich in giving away money before they grow old.

For the first time in more than a decade, the five biggest donors to U.S. charities in 2012 also include two other couples under the age of 40 -- Google (GOOG) co-founder Sergey Brin and his wife Anne Wojcicki, both 39; and Texas financiers John and Laura Arnold, both in their late 30s -- although octogenarian investor Warren Buffett ranked first on the list.

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"There's a real change in how people think about philanthropy. It used to be something people would do later in life, but now they're saying, 'I want to start doing good right away,' " said Stacy Palmer, editor of the Chronicle of Philanthropy, a newspaper and website that has ranked the nation's 50 biggest donors to charity every year since 2000.

The 28-year-old Zuckerberg has made the top-50 list once before, as has Brin, who donated $222.9 million to charity in 2012. But neither has been in the top five before. Other prominent Silicon Valley figures on this year's top 50 include Sequoia Capital chairman Michael Moritz, who gave $116.4 million; Oracle (ORCL) chairman Jeff Henley, who donated $50 million; and Oracle CEO Larry Ellison, who gave $45.6 million.

While the amount given by the top 50 still falls short of the total given before the 2008 recession, experts said many wealthy individuals are heeding a campaign by Buffett and Microsoft's Bill Gates, who are encouraging billionaires to share their wealth before they die.

"This is a new phenomenon of 'giving while living,' " said Patrick Rooney, an associate dean at the Indiana University School of Philanthropy. "Historically, people worked for most of their lives before they amassed sizable wealth, so it made sense for them to give it away as an end-of-life strategy."

The nation's biggest givers donated to a variety of causes, but they showed particular interest in funding community programs and medical research. The Chronicle noted an uptick in giving to community foundations like the one in Silicon Valley, which received its windfall in the form of Facebook stock from Zuckerberg and his wife, pediatrician Priscilla Chan.

Nationwide, giving to community foundations may have been fueled by uncertainty over whether federal tax laws might change in 2013. Some donors transferred funds to community foundations in 2012 so they could be sure of getting a tax benefit before the laws change, knowing the foundations would help them distribute the money in future years, said Teri Hansen, a Florida charity executive who chairs a national panel on community foundations.

But she also said foundations are making a strong argument for supporting local services at a time of government budget cuts. The Zuckerbergs have said they want to support health and education, although they haven't revealed specifically where the money will go.

"We're seeing more interest from large donors," added Hansen, who said groups like the Silicon Valley foundation can help identify worthy recipients for wealthy people who don't want to set up their own foundations to distribute funds.

Unlike Zuckerberg, Brin and his wife have their own foundation, to which they transferred $190 million of their fortune last year. The Brin Wojcicki Foundation supports local and national charities including the Human Rights Foundation and the San Francisco-based Tipping Point Community, which funds anti-poverty programs in the Bay Area.

"One of the big things for them is leverage. They put up $1 million last year" in a challenge grant "to help get other people involved in giving too," said Jen Pitts at Tipping Point Community, which funds health, education and other services in poor communities including East Palo Alto and the East Bay.

Brin and Wojcicki also gave $32.8 million last year to the Michael J. Fox Foundation for Parkinson's Research. Brin's mother has Parkinson's and he has said genetic testing shows he may be vulnerable to developing the disease.

Among other local givers, Ellison gave to research programs through his Ellison Medical Foundation. Oracle's Henley gave to his alma mater, UC Santa Barbara, while Moritz and his wife pledged $116 million to scholarships for poor students at the University of Oxford, which he attended.

Menlo Park financier George Roberts, who co-founded Kohlberg Kravis Roberts & Company, pledged $50 million to Claremont McKenna College. James Spilker, of Sunnyvale, who helped develop GPS technology, and his wife pledged $28 million to the Stanford School of Engineering.

Contact Brandon Bailey at 408-920-5022; follow him at Twitter.com/BrandonBailey.